Journal of Magnetism and Magnetic Materials 344 (2013) 207–210

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Journal of Magnetism and Magnetic Materials

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Adiabatic temperature change around coinciding first and second

order magnetic transitions in Mn3Ga(C0.85N0.15)
Ö. Çakır a, M. Acet b,n
a
Physics Department, Yıldız Technical University, Istanbul, Turkey
b
Experimentalphysik, Universität Duisburg-Essen, D-47048 Duisburg, Germany

art ic l e i nf o a b s t r a c t

Article history: The inverse magnetocaloric material in Mn3GaC relies on the presence of a first order antiferromagnetic–
Received 18 February 2013 ferromagnetic transition at around 160 K. Since Mn3GaN is antiferromagnetic, the partial substitution of
Received in revised form carbon by nitrogen in Mn3GaC enhances the antiferromagnetic exchange and shifts this transition to
28 May 2013
higher temperatures. At the Mn3Ga(C0.85N0.15) stoichiometry, the transition takes place at 180 K. The
Available online 11 June 2013
hysteresis at the transition reduces so that the inverse magnetocaloric effect is practically reversible. We
Keywords: study the magnetocaloric effect and the reversibility of the adiabatic temperature-change by magnetiza-
Magnetocaloric effect tion and direct temperature-change measurements up to field-changes of 5 T.
Magnetic entropy & 2013 Elsevier B.V. All rights reserved.
Adiabatic temperature change
Antiperovskite

Magnetic refrigeration technology based on the magnetocaloric
effect (MCE) has attracted much attention because of its potential
advantages such as environment-friendly and energy-efficient
virtues compared to traditional refrigeration technology. Gener-
ally, materials to be used in magnetic refrigeration technology
should demonstrate large magnetocaloric effects [1]. Large con-
ventional or inverse magnetocaloric effects associated with large
entropy changes ΔS are usually observed around first-order
magnetostructural transitions [2–5]. These are larger than those
observed around second-order magnetic transitions. However, the
disadvantage for practical applications of magnetic refrigeration
materials relying on magnetostructural transitions is the transition
hysteresis which causes irreversibilities in the adiabatic
temperature-change ΔT ad due to hysteresis losses. Nevertheless,
if the thermal hysteresis is sufficiently narrow, reversibility in ΔT ad
can be established [6,7].
Mn-based antiperovskite compounds in the form Mn3M C and
Mn3M N (M: Al, Zn, Ga, Ge, Sn, In) show a large variety of magnetic
ordering configurations and structural transitions and have been
extensively studied [8–11]. These materials are ordered in a cubic
symmetry with the Pm3m space group, whereby the C or N atoms
are located at the octahedral site at the cube-center. In some cases,
the hysteresis related to the transition in these materials can also
be small, so that it is particularly worth investigating various
compositional combinations of these materials to tailor the
n
Corresponding author.
E-mail address: mehmet.acet@uni-due.de.(M. Acet)
thermal range of the magnetostructural transition for magnetic
refrigerant technology applications [7].
Among the Mn-based antiperovskites, Mn3GaC has been parti-
cularly investigated in detail both from fundamental physical and
technological points of view. It undergoes a first-order antiferro-
magnetic (AF) to ferromagnetic (FM) transition at Tt ¼165 K and a
second-order FM to paramagnetic (PM) transition at TC ¼250 K
[12–18]. Without a change in the structure, an anomalous unit-cell
volume-increase by about 0.5% occurs when the temperature is
lowered through the AF–FM transition. Much effort has been spent
to shift the temperatures to chosen refrigeration temperature-
ranges. For example, partial replacement of Mn by Fe or Ni on
substitutional sites shifts Tt to lower temperatures while shifting
TC to higher temperatures [19,20]. In Mn3AlCx varying the carbon
content also varies Tt and TC [21]. The partial substitution of Ga by
Al introduces new magnetic states for which the transition
temperatures can be shifted by an external magnetic field [22].
Pressure can also shift the transition temperatures [23]. The
studies mentioned above have focused on the substitution of Mn
by another 3d element or the substitution of Ga by another main
group element. Studies on the partial replacement of the carbon
metalloid interstitial with nitrogen or boron are more limited in
Mn-based antiperovskite materials [24–26].
Mn3GaN is antiferromagnetic (AF) with an isotropic structure
[27], and earlier studies have shown that it has been possible to
control both Tt and TC of Mn3GaC by replacing the carbon
interstitial with nitrogen [24]. It has been shown that at a
concentration around x ¼0.10–0.20 in Mn3Ga(C1−xNx), Tt and TC
approach each other and practically coincide so that on increasing
temperature, the transition takes place from an AF state to an

0304-8853/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jmmm.2013.05.057
208 Ö. Çakır, M. Acet / Journal of Magnetism and Magnetic Materials 344 (2013) 207–210

enhanced paramagnetic (EPM) state, without any long-range FM

ordering setting in. The absence of long-range FM ordering could
lead to a decrease in the transition hysteresis and lower transi-
tional losses. On the other hand, a high-enough external magnetic-
field could stabilize long-range FM ordering, so that a field-
induced AF–FM transition can involve large entropy-changes
giving rise to large inverse magnetocaloric effects. Therefore, we
focus here on the hysteretic and magnetocaloric properties of a
sample with Mn3Ga(C0.85N0.15) stoichiometry and focus on the
reversibility of the direct adiabatic temperature-change, ΔT ad .
Direct ΔT ad measurements and the reversibility of ΔT ad on
repeatedly applying and removing the external magnetic field
give the ultimate test on the usefulness of the materials for MCE
applications. We investigate the magnetocaloric effect by deter-
mining the entropy-change from isothermal magnetization mea-
surements, M(H), and by direct adiabatic temperature-change,
Fig. 2. Temperature dependence of the magnetization under 5 mT (right scale) and
ΔT ad , measurements. ΔT ad was measured in a calorimeter with under 1, 3, and 5 T (left scale). Tt shifts with the applied field at a rate of −2.5 K T−1.
standard calorimetric techniques employing waiting times of The right-hand scale is for the data taken under 0.005 T.
about 10 min before and after applying the magnetic field to
account for nonadiabatic conditions. The magnetization measure-
ments were carried out using a superconducting quantum inter-
ference device magnetometer, and ΔT ad was measured directly in
a purpose-built calorimeter incorporating a 5 T superconducting
magnet.
First, Mn2N was obtained by flowing nitrogen gas over Mn
powder for 2 days at 850 1C. This was then mixed with Mn and C
powder and Ga pieces. They were pressed into a pellet and sealed
in a quartz tube under argon atmosphere. The sample was held at
800 1C for 5 days. X-ray powder diffraction (Fig. 1) verified the
antiperovskite structure with a lattice constant of 3.892 Å which is
somewhat smaller than the lattice constant 3.894 Å of Mn3GaC
[12,24]. A reflection related to excess graphite is indicated in the
figure.
The temperature-dependence of the magnetization M(T) is
shown in Fig. 2 in the temperature-range 5 ≤T ≤ 380 K and in
external magnetic fields of 0.005, 1, 3, and 5 T. The measurements
were taken with standard zero-field-cooled (ZFC) and field-cooled
(FC) protocols. As the temperature decreases from 380 K, M
increases tending to approach a FM state. However, before TC is
reached a transition to an AF state occurs at Tt, below which the
magnetization rapidly decreases. Tt shifts to lower temperatures
by about −2.5 K T−1. Since Tt and TC nearly coincide there is no
temperature-range for which long-range ferromagnetism is stable.

Fig. 3. The magnetization isotherms. (a) The isotherms in the vicinity of TI. (b) The
isotherm at 175 K obtained on increasing and decreasing field showing very weak
hysteresis, a property favorable for magnetic refrigeration.

The transition occurs between an AF and an EPM state. The data

Fig. 1. The X-ray diffraction pattern of Mn3Ga(C0.85N0.15). The reflections are related
to the cubic antiperovskite structure. A reflection related to excess graphite is
indicated in the figure.
taken under the higher fields show some residual ferromagnetism
so that M(T) is off-set close to 10 Am2 kg−1, unchanging under
measurement fields of 1–5 T, indicating that this value is about the
saturation value of the residual ferromagnet (this can also be seen
in Fig. 3 where M(H) initially rises steeply and eventually tends
toward saturation). Residual ferromagnetism acts as a conven-
tional magnetocaloric material, and therefore as a heat source
when a magnetic field is applied. This affects the measured ΔT ad of
the principal inverse magnetocaloric material in the sample, in a
manner that the temperature decrease on applying the field
becomes lower than the expected full value which a sample
without residual ferromagnetism would show. In Fig. 2, other
than the small difference in M(T) between the FC and ZFC states
for 0.005 T, no splitting is found in the data obtained in higher
 Ö. Çakır, M. Acet / Journal of Magnetism and Magnetic Materials 344 (2013) 207–210 209

Fig. 4. The temperature-dependence of the entropy-change calculated from

magnetization isotherms for field-changes of 1–4.8 T. Fig. 5. Temperature dependence of the adiabatic temperature-change in a field-
change of 3 T. Prior to each measurement, the sample was taken initially to 160 K.
The lines are guides.
fields. Thermal hysteresis is essentially absent so that this material
could be useful for magnetic refrigeration.
The magnetization isotherms for Mn3Ga(C0.85N0.15) are shown
in Fig. 3 in the temperature-range of the transition, where
metamagnetic-like behavior indicates the presence of field-
induced transformations from the AF state to the EPM state
(Fig. 3(a)). The initial rise in M(H) at low fields is due to residual
ferromagnetism. Its presence leads to a lower estimated value of
ΔS from the numerical integration of the Maxwell relationships. In
Fig. 3(b), we show M(H) on increasing and decreasing fields where
there is very little difference showing that the field-induced
transitional hysteresis is very weak. A similar weak hysteresis
would also be expected in the transition range if the magnetiza-
tion could be measured under adiabatic conditions.
The temperature-dependence of the entropy-change ΔS is
shown in Fig. 4 for field changes ranging from 1 to 4.8 T. ΔS is
positive in the range of the transition exhibiting the inverse
magnetocaloric effect and is negative above it showing the con-
ventional magnetocaloric effect. Around 4 T, ΔS reaches its max-
imum value of about 9 J kg−1 K−1.
To investigate the magnetocaloric effect more closely and to
examine the suitability of the sample as an inverse magnetocaloric
material we have measured the temperature-dependence of ΔT ad
directly in an adiabatic calorimeter. The temperature of the sample
is initially brought to 160 K and then raised to the desired
measuring temperature. The sample is then isolated from the
surroundings and the temperature is monitored for 600 s to
account for nonadiabatic conditions. The field is then increased
to 3 T in about 200 s, and the temperature is continuously
̃ K. ΔT ad
Fig. 6. Effect of field-cycling. (a) Field-cycling of a 5 T-magnetic field at 176
recorded. After the field reaches its maximum value, the tempera-
is reversible with a value of about 3 K. The lines through the data guide the
ture is further monitored for another 600 s, again to account for
determination of ΔT ad by standard calorimetric techniques. (b) Applying and
nonadiabatic conditions. Fig. 5 shows that at low temperatures, removing a field of 3 T. Up to 2.1 T the inverse magnetocaloric effect is present.
there is practically no temperature-change. In the region of the For μ0 H 42:1 T, the conventional magnetocaloric effect occurs.
transition, the inverse magnetocaloric effect is observed: the
sample cools on applying a field and warms on removing it. The
absolute value of ΔT is essentially the same when the field is magnetic refrigeration, however it is important to note here that
applied or removed at any given measuring temperature. This is the sample may not be useful at all temperatures within the
consistent with the narrow hysteresis related to the transition transition region. As shown in Fig. 6b, where the initial tempera-
seen in Figs. 2 and 3(b). At higher temperatures the sample is in ture is 182.1 K and where ΔT ad undergoes a 0–3–0 T cycle, the
the EPM state, and a reversible conventional magnetocaloric effect sample first shows the inverse magnetocaloric effect with a
of about 1 K is observed. temperature-drop of 0.43 K up to about 2.1 T, but then the sample
To examine the reversibility of ΔT ad closer, we have measured it warms again by 0.36 K as the field further increases to 3 T. On
cyclicly at about 176 K, which is close to the maximum value of removing the field at the 1500 s point, the process reverses. The
ΔT ad in Fig. 6. Fig. 6(a) shows the 0–5–0 T cyclic application of the cause of this effect is due to the shift of the transition temperature
magnetic field over several periods. The absolute value of ΔT ad due to applied field to a value lower than that of the measuring
remains constant at a value of about 3 K over all periods due to the temperature, so that the system enters into the EPM state already
narrow hysteresis in this sample. This property is favorable for at 2.1 T and shows the conventional magnetocaloric effect.
210 Ö. Çakır, M. Acet / Journal of Magnetism and Magnetic Materials 344 (2013) 207–210
Therefore the sample warms when the field is further increased up
from 2.1 to 3 T.
The cause of adiabatic cooling on applying a magnetic field, i.e.,
the inverse magnetocaloric effect is not fully understood. In the
case of the conventional magnetocaloric effect, applying a mag-
netic field causes a decrease in the magnetic entropy which is
balanced by an increase in the vibrational entropy accounting for
the observed warming, provided that the electronic entropy does
not change. A similar argument accounting for adiabatic cooling on
applying a magnetic field is not as straight forward. Adiabatic
cooling would require a decrease in the vibrational entropy. This
would then require the magnetic entropy to increase—which is
not possible other than in a paraprocess where the adiabatic
temperature-change is in the order of a tenth of a degree [1].
Therefore, instead of attempting to account for the observed
cooling, one can base the argument on the fact that cooling is
observed and provide an explanation for the possible changes in
the various contributions to the entropy.
In an adiabatic process the total entropy-change ΔStot is zero,
i.e.,
ΔStot ¼ ΔSvib þ ΔSm þ ΔSel ¼ 0;
where ΔSvib is the change in the vibrational entropy, ΔSm is the
change in the magnetic entropy, and ΔSel is the change in the
electronic entropy. Since cooling is observed in the inverse
magnetocaloric effect, Svib should decrease so that ΔSvib o 0. This
means that the sum of the other two terms should be positive
since the total entropy-change must be zero in an adiabatic
process. Indeed, if the system undergoes a thermally induced
magnetic transition from an AF to an EPM state, it cannot be
expected that ΔSel vanishes [7], so that the sum of ΔSm and ΔSel
has to compensate the observed decrease in ΔSvib to satisfy the
condition that ΔStot ¼ 0. What the individual signs of ΔSm and ΔSel
are cannot be deduced from these experiments. This could be one
way of looking at the inverse magnetocaloric effect problem.
However, we acknowledge the complexity of the issue of under-
standing the inverse magnetocaloric effect around a magnetos-
tructural phase transition especially when it comes to dealing with
the separability of the various entropy contributions.
Replacing carbon by nitrogen in Mn3GaC can increase Tt and
simultaneously decrease TC and narrow the transitional hysteresis.
The narrowing of the transitional hysteresis affects favorably the
reversibility of the MCE on cyclicly applying and removing
external magnetic fields. It is our further aim to undertake studies
involving the replacement of carbon with other interstitial metal-
loids to enhance and tailor the transitional properties of Mn-based
antiperovskite compounds, especially in relation to the narrowing
of the transitional hysteresis.
Acknowledgments
We thank S. Kılıç-Çetin for experimental assistance. This work
was supported by Deutsche Forschungsgemeinschaft (No.
SPP1599).
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